Multilayer ceramic capacitor

ABSTRACT

A multilayer ceramic capacitor includes a ceramic main body including an inner layer portion including third ceramic layers and a plurality of inner electrodes arranged at interfaces between the third ceramic layers, and first and second outer layer portions respectively including first and second ceramic layers, the first and second ceramic layers being arranged vertically so as to sandwich the inner layer portion. The third ceramic layers and the first and second outer layer portions contain a perovskite-type compound represented by ABO 3  where A contains one or more of Ba, Sr, and Ca, B contains one or more of Ti, Zr, and Hf, and O represents oxygen) as a main component. Where a rare-earth element concentration (C R ) in the third ceramic layers is compared to a rare-earth element concentration (C r ) in outermost layer portions including at least outermost surfaces of the first and second outer layer portions, C R &gt;C r  (inclusive of C r =0).

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a multilayer ceramic capacitorcontaining a dielectric ceramic material.

2. Description of the Related Art

In general, multilayer ceramic capacitors each include a ceramic mainbody and outer electrodes, as described in Japanese Unexamined PatentApplication Publication No. 2008-081351. The ceramic main body includestwo main surfaces opposite to each other, two side surfaces opposite toeach other, and two end surfaces opposite to each other. The outerelectrodes are provided on the two respective end surfaces of theceramic main body.

The ceramic main body is a multilayer body that includes an inner layerportion and outer layer portions. The inner layer portion includes aplurality of ceramic layers for inner layers and a plurality of innerelectrodes arranged at the interfaces between the plurality of ceramiclayers for the inner layers. The outer layer portions include aplurality of ceramic layers for outer layers, the plurality of ceramiclayers for the outer layers being arranged vertically so as to sandwichthe inner layer portion. The inner electrodes are electrically connectedto the outer electrodes.

With respect to multilayer ceramic capacitors, as trends toward areduction in the thickness of individual ceramic layers and an increasein the number of ceramic layers progress, rare-earth elements are oftenadded in order to stabilize the temperature characteristics ofcapacitance and to ensure the high-temperature load life over the longterm in terms of insulation resistance.

Rare-earth elements, however, tend to concentrate at ceramic boundariesor segregated phases. Rare-earth elements are easily eluted in awater-soluble flux. Thus, resistance to elution in the water-solubleflux is disadvantageously reduced.

For this reason, in the case where such a multilayer ceramic capacitoris mounted, a ceramic component can be eluted in an organic acidcontained in a water-soluble flux used for soldering. A ceramic mainbody includes inner electrodes (metal) and a ceramic material having adifferent linear thermal expansion coefficient from that of the innerelectrodes, thus resulting in residual stress. The inner electrodes aretwo-dimensionally supported by outer layer portions. Thus, the outerlayer portions receive relatively high residual stress, compared toportions of the ceramic main body at which the inner electrodes are notlocated, the portions of the ceramic main body being adjacent to bothside surfaces of the ceramic main body on each of the ceramic layers forthe inner layers. Accordingly, in the case where a component in theouter layer portions is eluted in the water-soluble flux to embrittlethe outer layer portions, changes that occur over time after soldermounting disadvantageously cause a structural defect.

SUMMARY OF THE INVENTION

Preferred embodiments of the present invention provide a multilayerceramic capacitor having a structure in which elution in an organic acidis inhibited while electrical characteristics and reliability areensured.

A multilayer ceramic capacitor according to a preferred embodiments ofthe present invention includes a ceramic main body that includes aninner layer portion including third ceramic layers, the plurality ofceramic layers being stacked, and the inner layer portion including aplurality of inner electrodes arranged at a plurality of interfacesbetween the third ceramic layers, and first and second outer layerportions respectively including first and second ceramic layers, thefirst and second ceramic layers being arranged vertically so as tosandwich the inner layer portion, and outer electrodes arranged on theexterior surface of the ceramic main body and electrically connected tothe inner electrodes, in which the third ceramic layers contain aperovskite-type compound represented by ABO₃ (where A contains one ormore of Ba, Sr, and Ca; and B contains one or more of Ti, Zr, and Hf;and O represents oxygen) as a main component and a rare-earth element,an outermost layer portion including at least an outermost surface of atleast one of the first and second outer layer portions contains aperovskite-type compound represented by A′B′O₃ (where A′ contains one ormore of Ba, Sr, and Ca; B′ contains one or more of Ti, Zr, and Hf; and Orepresents oxygen) as a main component, and where a rare-earth elementconcentration (C_(R)) in the third ceramic layers is compared to arare-earth element concentration (C_(r)) in the outermost layer portion,C_(R)>C_(r) (inclusive of C_(r)=0).

Here, the rare-earth element concentration (C_(R)) in the third ceramiclayers is a rare-earth element content expressed in units of parts bymole with respect to 100 parts by mole of the total amount of Ti, Zr,and Hf that are the B-site components in ABO₃ in the third ceramiclayers. The rare-earth element concentration (C_(r)) in the outermostlayer portion is a rare-earth element content in units of parts by molewith respect to 100 parts by mole of the total amount of Ti, Zr, and Hfthat are the B-site components in A′B′O₃ in the outermost layer portion.

In the multilayer ceramic capacitor according to a preferred embodimentof the present invention, preferably, the rare-earth elementconcentration (C_(R)) in the third ceramic layers is about 0.3 parts bymole or more with respect to 100 parts by mole of the total amount ofTi, Zr, and Hf that are the B-site components in ABO₃ in the thirdceramic layers, and the rare-earth element concentration (C_(r)) in theoutermost layer portion is less than about 0.3 parts by mole withrespect to 100 parts by mole of the total amount of Ti, Zr, and Hf thatare the B-site components in A′B′O₃ in the outermost layer portion.

In the multilayer ceramic capacitor according to a preferred embodimentof the present invention, preferably, the molar quantities of metalelement components except the rare-earth element in the third ceramiclayers are equal or substantially equal to those in the outermost layerportion.

In the multilayer ceramic capacitor according to a preferred embodimentof the present invention, preferably, where a Mn concentration (C_(M))in the third ceramic layers is compared to a Mn concentration (C_(m)) inthe outermost layer portion, C_(M)>C_(m) (inclusive of C_(m)=0).

In the multilayer ceramic capacitor according to a preferred embodimentof the present invention, preferably, where the Mn concentration in thethird ceramic layers is denoted by a parts by mole with respect to 100parts by mole of the total amount of Ti, Zr, and Hf that are the B-sitecomponents in ABO₃ in the third ceramic layers and where the Mnconcentration in the outermost layer portion is denoted by b parts bymole with respect to 100 parts by mole of the total amount of Ti, Zr,and Hf that are the B-site components in A′B′O₃ in the outermost layerportions, a≧ about 0.08 parts by mole, and b≦ about 0.9×a (b is about90% or less of a).

In the multilayer ceramic capacitor according to a preferred embodimentof the present invention, preferably, the molar quantities of metalelement components except the rare-earth element and Mn in the thirdceramic layers are equal or substantially equal to those in theoutermost layer portion.

In the multilayer ceramic capacitor according to a preferred embodimentof the present invention, where the rare-earth element concentration(C_(R)) in the third ceramic layers is compared to the rare-earthelement (C_(r)) in the outermost layer portion, C_(R)>C_(r) (inclusiveof C_(r)=0). The electrical characteristics and reliability of themultilayer ceramic capacitor are influenced by the third ceramic layers.Thus, a multilayer ceramic capacitor having excellent resistance toelution is provided while the electrical characteristics and thereliability are ensured. Moreover, a reduction in the concentration ofthe rare-earth element, which is expensive, in the outermost layerportion provides an inexpensive multilayer ceramic capacitor.

In the multilayer ceramic capacitor according to a preferred embodimentof the present invention, where the rare-earth element concentration(C_(R)) in the third ceramic layers is about 0.3 parts by mole or morewith respect to 100 parts by mole of the total amount of Ti, Zr, and Hfthat are the B-site components in ABO₃ in the third ceramic layers andwhere the rare-earth element concentration (C_(r)) in the outermostlayer portion is less than about 0.3 parts by mole with respect to 100parts by mole of the total amount of Ti, Zr, and Hf that are the B-sitecomponents in A′B′O₃ in the outermost layer portion, a multilayerceramic capacitor having excellent resistance to elution is providedwhile the electrical characteristics and the reliability are ensured.

In the multilayer ceramic capacitor according to a preferred embodimentof the present invention, where a Mn concentration (C_(M)) in the thirdceramic layers is compared to a Mn concentration (C_(m)) in theoutermost layer portion, if C_(M)>C_(m) (inclusive of C_(m)=0), thecolor of the main surfaces of the ceramic main body differs from thecolor of the side surfaces of the ceramic main body.

Where the Mn concentration in the third ceramic layers is denoted by aparts by mole with respect to 100 parts by mole of the total amount ofTi, Zr, and Hf that are the B-site components in ABO₃ in the ceramiclayers for the inner layers and where the Mn concentration in theoutermost layer portion is denoted by b parts by mole with respect to100 parts by mole of the total amount of Ti, Zr, and Hf that are theB-site components in A′B′O₃ in the outermost layer portions, if a≧ about0.08 parts by mole, and b≦ about 0.9×a (b is about 90% or less of a),the color of the main surfaces of the ceramic main body further differsfrom the color of the side surfaces of the ceramic main body. In thiscase, the main surfaces can be visually discriminated from the sidesurfaces, so that the stacking direction of the inner electrodes iscapable of being determined from the appearance of the multilayerceramic capacitor. It is thus possible to mount the multilayer ceramiccapacitor with a desired positional relationship between a substrate andthe inner electrodes of the multilayer ceramic capacitor.

According to a preferred embodiment of the present invention, amultilayer ceramic capacitor includes a ceramic main body including afirst outer layer portion including first ceramic layers, a second outerlayer portion including second ceramic layers, an inner layer portionincluding third ceramic layers and inner electrodes arranged at aplurality of interfaces between at least some of the third ceramiclayers, and outer electrodes arranged on surfaces of the ceramic mainbody and electrically connected to the inner electrodes, wherein thefirst outer layer portion and the second outer layer portion arearranged vertically so as to sandwich the inner layer portiontherebetween, the third ceramic layers contain a perovskite-typecompound represented by ABO₃, where A contains one or more of Ba, Sr,and Ca; B contains one or more of Ti, Zr, and Hf; and O representsoxygen, and a rare-earth element, an outermost layer portion of at leastone of the first and the second outer layer portions including at leasta portion of a surface of the ceramic main body contains aperovskite-type compound represented by A′B′O₃, where A′ contains one ormore of Ba, Sr, and Ca; B′ contains one or more of Ti, Zr, and Hf; and Orepresents oxygen, and optionally a rare-earth element that is the sameor different as the rare-earth element of the third ceramic layers, amol concentration (C_(R)) of the rare-earth element in the third ceramiclayers is greater than a mol concentration (C_(r)) of the rare-earthelement in the outermost layer portion, C_(R)>C_(r) inclusive ofC_(r)=0, the mol concentration (C_(R)) is about 0.3 parts by mole ormore with respect to 100 parts by mole of total amount of Ti, Zr, and Hfincluded in the third ceramic layers, and the mol concentration (C_(r))is less than about 0.3 parts by mole with respect to 100 parts by moleof total amount of Ti, Zr, and Hf included in the outermost layerportions.

Alternatively in the preferred embodiment of the present inventiondescribed in the preceding paragraph, an entirety of the surface of theceramic main body preferably contains the perovskite-type compoundrepresented by A′B′O₃.

According to a preferred embodiment of the present invention, amultilayer ceramic capacitor includes a ceramic main body including afirst outer layer portion including first ceramic layers, a second outerlayer portion including second ceramic layers, an inner layer portionincluding third ceramic layers and inner electrodes arranged at aplurality of interfaces between at least some of the third ceramiclayers, and outer electrodes arranged on surfaces of the ceramic mainbody and electrically connected to the inner electrodes, wherein thefirst outer layer portion and the second outer layer portion arearranged vertically so as to sandwich the inner layer portiontherebetween, the third ceramic layers contain a perovskite-typecompound represented by ABO₃, where A contains one or more of Ba, Sr,and Ca; B contains one or more of Ti, Zr, and Hf; and O representsoxygen, a rare-earth element, and Mn, an outermost layer portion of atleast one of the first and the second outer layer portions including aportion of a surface of the ceramic main body contains a perovskite-typecompound represented by A′B′O₃, where A′ contains one or more of Ba, Sr,and Ca; B′ contains one or more of Ti, Zr, and Hf; and O representsoxygen, and optionally Mn and a rare-earth element that is the same ordifferent as the rare-earth element of the third ceramic layers, a molconcentration (C_(R)) of the rare-earth element in the third ceramiclayers is greater than a mol concentration (C_(r)) of the rare-earthelement in the outermost layer portion, C_(R)>C_(r) inclusive ofC_(r)=0, and a mol concentration (C_(M)) of Mn in the third ceramiclayers is greater than a mol concentration (C_(m)) of Mn in theoutermost layer portion, C_(M)>C_(m) (inclusive of C_(m)=0).

Alternatively in the preferred embodiment of the present inventiondescribed in the preceding paragraph, an entirety of the surface of theceramic main body preferably contains the perovskite-type compoundrepresented by A′B′O₃.

According to a preferred embodiment of the present invention, amultilayer ceramic capacitor includes a ceramic main body a first outerlayer portion including first ceramic layers, a second outer layerportion including second ceramic layers, an inner layer portionincluding third ceramic layers and inner electrodes arranged at aplurality of interfaces between at least some of the third ceramiclayers, and outer electrodes arranged on surfaces of the ceramic mainbody and electrically connected to the inner electrodes, wherein thefirst outer layer portion and the second outer layer portion arearranged vertically so as to sandwich the inner layer portiontherebetween, the third ceramic layers contain a perovskite-typecompound represented by ABO₃, where A contains one or more of Ba, Sr,and Ca; B contains one or more of Ti, Zr, and Hf; and O representsoxygen, a rare-earth element, and Mn, and only the second outer layerportion of the first and second outer layer portions includes each offeatures (a), (b), (c) and (d):

(a) an outermost layer portion of at least one of the first and thesecond outer layer portions including a portion of a surface of theceramic main body contains a perovskite-type compound represented byA′B′O₃, where A′ contains one or more of Ba, Sr, and Ca, B′ contains oneor more of Ti, Zr, and Hf, and O represents oxygen, and optionally Mnand a rare-earth element that is the same or different than therare-earth element of the third ceramic layers;

(b) a mol concentration (C_(R)) of the rare-earth element in the thirdceramic layers is greater than a mol concentration (C_(r)) of therare-earth element in the outermost layer portion, C_(R)>C_(r),inclusive of C_(r)=0; and

(c) a mol concentration (C_(M)) of Mn in the third ceramic layers isgreater than a mol concentration (C_(m)) of Mn in the outermost layerportion, C_(M)>C_(m) (inclusive of C_(m)=0); and

(d) an intermediate ceramic layer is arranged between the outermostlayer portion and the inner layer portion, and the intermediate ceramiclayer has a different composition from the outermost layer portion.

In the preferred embodiment of the present invention described in thepreceding paragraph, it is preferable that the first outer layer portionincludes any one, two or three of features (a), (b), (c) and (d), andwherein feature (a) is an outermost layer portion of the first outerlayer portion including a portion of a surface of the ceramic main bodycontains a perovskite-type compound represented by A′B′O₃, where A′contains one or more of Ba, Sr, and Ca, B′ contains one or more of Ti,Zr, and Hf, and O represents oxygen, and optionally Mn and a rare-earthelement that is the same or different than the rare-earth element of thethird ceramic layers.

Alternatively in the preferred embodiment of the present inventiondescribed in the preceding two paragraphs, an entirety of the surface ofthe ceramic main body preferably contains the perovskite-type compoundrepresented by A′B′O₃.

Alternatively in the preferred embodiment of the present inventiondescribed in the preceding two paragraphs, the mol concentration (Cr) ofthe rare-earth element in the outermost layer portion preferably issmaller than a mol concentration of the rare-earth element in theoutermost layer portion of the first outer layer portion including theportion of the surface of the ceramic main body.

According to various preferred embodiments of the present invention,first and second ceramic layers having excellent resistance to elutionare provided. Thus, a multilayer ceramic capacitor having a structure inwhich elution in an organic acid is inhibited is provided whileelectrical characteristics and reliability are ensured.

The above and other elements, features, steps, characteristics andadvantages of the present invention will become more apparent from thefollowing detailed description of the preferred embodiments withreference to the attached drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view of a multilayer ceramic capacitor accordingto a preferred embodiment of the present invention.

FIG. 2 is a schematic cross-sectional view of the internal structure ofthe multilayer ceramic capacitor illustrated in FIG. 1.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

A multilayer ceramic capacitor according to various preferredembodiments of the present invention and a method for producing themultilayer ceramic capacitor will be described below.

FIG. 1 is a perspective view of a multilayer ceramic capacitor accordingto a preferred embodiment of the present invention. FIG. 2 is aschematic cross-sectional view illustrating the internal structure ofthe multilayer ceramic capacitor. A multilayer ceramic capacitor 1includes a ceramic main body 10, and outer electrodes 26 and 28 arrangedon left and right end portions of the ceramic main body 10.

The ceramic main body 10 includes a main surface (upper surface) 10 aand a main surface (surface to be mounted) 10 b, which are opposite toeach other, a side surface 10 c and a side surface 10 d, which areopposite to each other, an end surface 10 e and an end surface 10 f,which are opposite to each other.

The ceramic main body 10 has a multilayer structure that includes aninner layer portion 12 and first and second outer layer portions 14. Theinner layer portion 12 includes a plurality of ceramic layers 16 forinner layers, hereinafter referred to as third ceramic layers, and aplurality of inner electrodes 18 and 19 arranged at interfaces betweenthe third ceramic layers 16. The first and second outer layer portions14 respectively include first and second ceramic layers 20 a and 20 b,the first and second ceramic layers 20 a and 20 b being arrangedvertically so as to sandwich the inner layer portion 12.

The inner electrodes 18 and the inner electrodes 19 are arranged so asto oppose each other with the third ceramic layers 16 interposedtherebetween in the thickness direction, the third ceramic layers 16preferably being composed of a dielectric substance. Electrostaticcapacitance is generated in portions where the inner electrodes 18 andthe inner electrodes are arranged to oppose each other with the thirdceramic layers 16 interposed therebetween. The inner electrodes 18 and19 are preferably composed of, for example, Cu, Ni, or an alloy of thesemetals.

The left end portion of each of the inner electrodes 18 extends to theleft end surface 10 e of the ceramic main body 10 and is electricallyconnected to the outer electrodes 26. The right end portion of each ofthe inner electrodes 19 extends to the right end surface 10 f of theceramic main body 10 and is electrically connected to the outerelectrode 28.

The main component of the third ceramic layers 16 included in the innerlayer portion 12 is preferably a perovskite-type compound represented byABO₃, where A contains one or more of Ba, Sr, and Ca; B contains one ormore of Ti, Zr, and Hf; and O represents oxygen. For example, the maincomponent of the third ceramic layers 16 may preferably be aperovskite-type compound, for example, BaTiO₃ or CaZrO₃.

In the first and second ceramic layers 20 a and 20 b, some layersincluding the outermost layers are ceramic layers 22 a and 22 b eachpreferably having a low rare-earth element concentration and definingthe outermost layer portions. The remaining layers are intermediateceramic layers 24 a and 24 b each preferably containing the same maincomponent as the third ceramic layers 16. However, all of the layers ofthe first and second ceramic layers 20 a and 20 b may be the ceramiclayers 22 a and 22 b each having a low rare-earth element concentrationand defining the outermost layer portions. The ceramic layer 22 a or 22b having a low rare-earth element concentration and defining theoutermost layer portion may be arranged in only one of the ceramiclayers 20 a and 20 b for the outer layers. The intermediate ceramiclayers 24 a and 24 b may contain a different main component from thethird ceramic layers 16.

The main component of the ceramic layers 22 a and 22 b each having a lowrare-earth element concentration and defining the outermost layerportions is preferably a perovskite-type compound represented by A′B′O₃,where A′ contains one or more of Ba, Sr, and Ca; B′ contains one or moreof Ti, Zr, and Hf; and O represents oxygen. For example, the maincomponent of the ceramic layers 22 a and 22 b may preferably be aperovskite-type compound, such as, BaTiO₃ or CaZrO₃.

When a rare-earth element concentration (C_(R)) in the third ceramiclayers 16 included in the inner layer portion 12 is compared to arare-earth element concentration (C_(r)) in the ceramic layers 22 a and22 b, C_(R)>C_(r) (inclusive of C_(r)=0). Examples of the rare-earthelement (R) include Dy, Gd, Y, and La.

Where the third ceramic layers 16 included in the inner layer portion 12have a rare-earth element (R) content of about 0.3 parts by mole or morewith respect to 100 parts by mole of the total amount of Ti, Zr, and Hfthat are the B-site components in the perovskite-type compound (ABO₃),the rare-earth element (R) concentration in the ceramic layers 22 a and22 b included in the first and second outer layer portions 14 ispreferably less than about 0.3 parts by mole with respect to 100 partsby mole of the total amount of Ti, Zr, and Hf that are the B-sitecomponents in the perovskite-type compound (A′B′O₃).

It is preferable that the molar quantities of metal element componentsexcept the rare-earth element in the third ceramic layers 16 included inthe inner layer portion 12 be equal or substantially equal to those inthe ceramic layers 22 a and 22 b. In this case, the production processis simplified. Where the third ceramic layers are in contact with theceramic layers 22 a and 22 b, a reduction in bonding strength isinhibited.

Where a Mn concentration (C_(M)) in the third ceramic layers 16 includedin the inner layer portion 12 is compared to a Mn concentration (C_(m))in the ceramic layers 22 a and 22 b being included in the first andsecond outer layer portions 14, it is preferable that C_(M)>C_(m)(inclusive of C_(m)=0).

Where the Mn concentration in the third ceramic layers 16 included inthe inner layer portion 12 is denoted by a parts by mole with respect to100 parts by mole of the total amount of Ti, Zr, and Hf that are theB-site components in ABO₃ and where the Mn concentration in the ceramiclayers 22 a and 22 b included in the first and second outer layerportions 14 is denoted by b parts by mole with respect to 100 parts bymole of the total amount of Ti, Zr, and Hf that are the B-sitecomponents in A′B′O₃, it is preferable that a≧ about 0.08 parts by moleand that b≦ about 0.9×a (b is about 90% or less of a).

It is preferable that the molar quantities of metal element componentsexcept the rare-earth element and Mn in the third ceramic layers 16included in the inner layer portion 12 be equal or substantially equalto those in the ceramic layers 22 a and 22 b. In this case, theproduction process is simplified. Where the third ceramic layers 16 arein contact with the ceramic layers 22 a and 22 b, a reduction in bondingstrength is inhibited.

In the multilayer ceramic capacitor 1 illustrated in FIG. 2, therare-earth element concentration in the ceramic layers 22 a and 22 bincluded in the first and second outer layer portions 14 is preferablylower than the rare-earth element concentration in the third ceramiclayers 16. Thus, the ceramic layers 22 a and 22 b are less likely to bedissolved in an organic acid, thereby resulting in the first and secondceramic layers 20 a and 20 b having excellent resistance to elution.

Regarding the various features discussed above, for convenience ofdescription, the following features will be referred to as features (a),(b), (c) and (d):

(a) an outermost layer portion of at least one of the first and thesecond outer layer portions including a portion of a surface of theceramic main body contains a perovskite-type compound represented byA′B′O₃, where A′ contains one or more of Ba, Sr, and Ca, B′ contains oneor more of Ti, Zr, and Hf, and O represents oxygen, and optionally Mnand a rare-earth element that is the same or different than therare-earth element of the third ceramic layers;

(b) a mol concentration (C_(R)) of the rare-earth element in the thirdceramic layers is greater than a mol concentration (C_(r)) of therare-earth element in the outermost layer portion, C_(R)>C_(r),inclusive of C_(r)=0; and

(c) a mol concentration (C_(M)) of Mn in the third ceramic layers isgreater than a mol concentration (C_(m)) of Mn in the outermost layerportion, C_(M)>C_(m) (inclusive of C_(m)=0); and

(d) an intermediate ceramic layer is arranged between the outermostlayer portion and the inner layer portion, and the intermediate ceramiclayer has a different composition from the outermost layer portion.

In one preferred embodiment of the present invention, only the secondouter layer portion of the first and second outer layer portionsincludes each of features (a), (b), (c) and (d).

In another preferred embodiment of the present invention, the firstouter layer portion includes any one, two or three of features (a), (b),(c) and (d), and wherein feature (a) is an outermost layer portion ofthe first outer layer portion including a portion of a surface of theceramic main body contains a perovskite-type compound represented byA′B′O₃, where A′ contains one or more of Ba, Sr, and Ca, B′ contains oneor more of Ti, Zr, and Hf, and O represents oxygen, and optionally Mnand a rare-earth element that is the same or different than therare-earth element of the third ceramic layers.

Feature (a) described above preferably is configured such that only aportion of a surface of the ceramic main body contains a perovskite-typecompound represented by A′B′O₃.

However, it is also possible that an entirety of the surface of theceramic main body contains the perovskite-type compound represented byA′B′O₃.

In addition, it is also possible that the mol concentration (Cr) of therare-earth element in the outermost layer portion is smaller than a molconcentration of the rare-earth element in the outermost layer portionof the first outer layer portion including the portion of the surface ofthe ceramic main body.

In the multilayer ceramic capacitor 1 illustrated in FIG. 2, where theMn concentration in the ceramic layers 22 a and 22 b included in theouter layer portions 14 is lower than the Mn concentration in the thirdceramic layers 16 included in the inner layer portion 12, the color ofthe main surfaces 10 a and 10 b (the ceramic layers 22 a and 22 b) ofthe ceramic main body 10 is lighter than that of the side surfaces 10 cand 10 d (primarily, the third ceramic layers 16 included in the innerlayer portion 12). The different colors are easily visuallydiscriminable. Thus, the direction of the multilayer ceramic capacitor 1is discriminable by observing the multilayer ceramic capacitor 1 with,for example, an image-pickup camera. Thus, the mounting direction can beeasily determined and aligned.

To enable the main surfaces 10 a and 10 b of the ceramic main body 10 tohave a different color from that of the side surfaces 10 c and 10 d, forexample, V may also be used as an element whose content in the ceramiclayers 22 a and 22 b is different from that in the third ceramic layers16. Mn is more preferable because of its larger difference in colorcorresponding to the difference in content.

As a result, for example, all of the multilayer ceramic capacitors 1preferably are mounted such that the inner electrodes 18 and 19 areparallel or substantially parallel to a printed circuit board (printedcircuit substrate). Thus, the value of stray capacitance generatedbetween the inner electrodes 18 and 19 and the printed circuit board isless likely to vary from lot to lot, thus reducing variations in theelectrical characteristics of the mounted multilayer ceramic capacitors1.

A non-limiting example of a method for producing the multilayer ceramiccapacitor 1 will be described below.

A BaCO₃ powder and a TiO₂ powder are weighed such that the Ba/Ti ratiois 1.000. They are wet-mixed using a ball mill. The resulting slurrymixture is dried and then heated to about 1050° C., thereby producing amain-component BaTiO₃ powder having a specific surface area of 2.9 m²/g.

Next, Dy₂O₃, MnCO₃, MgCO₃, BaCO₃, and SiO₂ are prepared as additivepowders. Then, about 0.15 parts by mole of Dy₂O₃, about 0.3 parts bymole of MnCO₃, about 1.0 part by mole of MgO, about 1.0 part by mole ofBaCO₃, and about 1.5 parts by mole of SiO₂ are added thereto withrespect to 100 parts by mole of the main-component BaTiO₃ powder. Theresulting mixture is wet-mixed using a ball mill together with deionizedwater defining and serving as a dispersion medium, thus providing aslurry.

The removal of water in the slurry results in a dry powder. The drypowder is size-selected to provide a ceramic raw-material powder forinner layers. A polybutyral-based binder and a plasticizer are added tothe ceramic raw-material powder for the inner layers. Then a dispersionmedium mixture of toluene and ethyl alcohol is added thereto. Theresulting mixture is wet-mixed using a ball mill, thereby preparing aslurry for sheet formation. The slurry for sheet formation is formedinto a sheet shape using a gravure coater, thereby providing greensheets for inner layers, and the green sheets each having a thickness ofabout 3.3 μm. The green sheets for the inner layers are fired to providethe ceramic layers 16 for the inner layers, the ceramic layers 16 eachhaving a thickness of about 2.8 μm.

A main-component BaTiO₃ powder is prepared by the foregoing method.Dy₂O₃, MnCO₃, MgCO₃, BaCO₃, and SiO₂ are prepared as additive powders.Then, about 0.1 parts by mole of Dy₂O₃, about 0.3 parts by mole ofMnCO₃, about 1.0 part by mole of MgO, about 1.0 part by mole of BaCO₃,and about 1.5 parts by mole of SiO₂ are added with respect to 100 partsby mole of BaTiO₃. A polybutyral-based binder and a plasticizer areadded to the weighed powders. Then toluene and ethyl alcohol are addedthereto. The resulting mixture is wet-mixed using a ball mill, therebypreparing a slurry for sheet formation. The slurry for sheet formationis formed into a sheet shape using a gravure coater, thereby providinggreen sheets each having a low rare-earth element concentration.

A conductive paste containing Ni as a main component is applied byscreen printing on the green sheets for the inner layers, therebyforming conductive paste film (conductor pattern) to be formed into theinner electrodes 18 and 19. Then, 316 sheets of the green sheets, onwhich the conductive paste films have been formed, for the inner layersare stacked such that end portions of the conductive paste films extendalternately in opposite directions.

The green sheet layers for the outer layers are stacked vertically so asto sandwich the stacked green sheets for the inner layers. That is, thegreen sheets for the outer layers are stacked to a thickness of about180 μm, the green sheets being composed of the same or substantially thesame material as the green sheets for the inner layers and not includinga conductive paste film. The green sheets each having a low rare-earthelement concentration are stacked to a thickness of about 40 μm on theouter side portions of the stacked green sheets for the outer layers.This results in a green ceramic main body 10 to be formed into the mainbody of the multilayer ceramic capacitor 1.

The green ceramic main body 10 is cut into a predetermined product size.The cut green ceramic main body 10 is heat-treated at 280° C. in a N₂atmosphere, thereby burning and removing the binder. The temperature ofthe green ceramic main body 10 is increased to 1280° C. at a rate oftemperature increase of 5° C./min at 800° C. or higher in a reducingatmosphere of N₂—H₂—H₂O gas. The green ceramic main body 10 is held at1280° C. for 100 minutes for firing, thereby resulting in the sinteredceramic main body 10.

The green sheets for the inner layers, the green sheets for the outerlayers, the green sheets each having a low rare-earth elementconcentration, and the conductive paste films are co-fired. As a result,the green sheets for the inner layers are formed into the third ceramiclayers 16. The green sheets each having a low rare-earth elementconcentration are formed into the ceramic layers 22 a and 22 b eachhaving a thickness of about 30 μm, the ceramic layers 22 a and 22 bdefining the outermost layer portions. The green sheets for the outerlayers are formed into the intermediate ceramic layers 24 a and 24 beach having a thickness of about 150 μm. The conductive paste films areformed into the inner electrodes 18 and 19. The sintered ceramic mainbody 10 is about 3.1 mm long, about 1.5 mm wide, and about 1.5 mm highand has a prism shape with a square cross-sectional shape.

A Cu paste is applied to the end surfaces 10 e and 10 f of the sinteredceramic main body 10. The sintered ceramic main body 10 is heated to800° C. in a N₂ atmosphere to bake the Cu paste, thereby forming theouter electrodes 26 and 28 electrically connected to the innerelectrodes 18 and 19. Then Ni—Sn coatings are formed by wet plating onthe surface layers of the outer electrodes 26 and 28, thereby providinga multilayer ceramic capacitor.

There are various non-limiting examples of multilayer ceramic capacitorshaving various sizes, for example, a size of about 3.2 mm long, about1.6 mm wide, and about 1.6 mm high, a size of about 1.0 mm long, about0.5 mm wide, and about 0.5 mm high, and a size of about 1.0 mm long,about 0.5 mm wide, and about 0.3 mm high. The present invention isapplicable to these multilayer ceramic capacitors.

Examples and Comparative Examples

Multilayer ceramic capacitors 1 according to examples and comparativeexamples were produced by the production method described in theforegoing preferred embodiments of the present invention, except foraspects described below and the amounts of Dy₂O₃, MnCO₃, MgO, SiO₂,Gd₂O₃, Y₂O₃, and La₂O₃ added in each layer.

An evaluation of the characteristics was conducted. Table 1 describesthe amounts of metal elements (Dy, Mn, Mg, Si, Gd, Y, and La) in Dy₂O₃,MnCO₃, MgO, SiO₂, Gd₂O₃, Y₂O₃, and La₂O₃ added in each layer withrespect to 100 parts by mole of the total amount of the B-sitecomponents (Ti, Zr, and Hf) in the main-component powder. Thecomposition of the intermediate ceramic layers was the same orsubstantially the same as that of the ceramic layers for the innerlayers.

In Example 1 and Example 2, all of the layers in the first and secondceramic layers 20 a and 20 b were defined by the ceramic layers 22 a and22 b each having a low rare-earth element concentration, the first andsecond ceramic layers 20 a and 20 b being included in the outer layerportions 14 and being arranged vertically. The ceramic layers 22 a and22 b (that is, the first and second ceramic layers 20 a and 20 b) eachhad a thickness of about 220 μm prior to firing.

In Example 3, regarding the first and second ceramic layers 20 a and 20b, the first and second ceramic layers 20 a and 20 b being included inthe outer layer portions 14 and being arranged vertically, some of thelayers including the outermost layers were defined by the ceramic layers22 a and 22 b having a low rare-earth element concentration. Theremaining layers were defined by the intermediate ceramic layers 24 aand 24 b. The ceramic layers 22 a and 22 b each had a thickness of about40 μm prior to firing. The intermediate ceramic layers 24 a and 24 beach had a thickness of about 180 μm prior to firing. Thus, the firstand second ceramic layers 20 a and 20 b each had a thickness of about220 μm prior to firing.

In Example 4, all of the layers in the first ceramic layer 20 a weredefined by the intermediate ceramic layers 24 a, the first ceramic layer20 a being included in the outer layer portion 14 and being arranged atthe upper side portion. The intermediate ceramic layers 24 a (that is,the first ceramic layer 20 a) had a thickness of about 220 μm prior tofiring. Meanwhile, some layers including the outermost layer in thesecond ceramic layer 20 b were defined by the ceramic layers 22 b havinga low rare-earth element concentration and defining the outermost layerportion, the second ceramic layer 20 b being included in the outer layerportion 14 and being arranged at the lower side portion. The remaininglayers were defined by the intermediate ceramic layers 24 b. The ceramiclayers 22 b had a thickness of about 180 μm prior to firing. Theintermediate ceramic layers 24 b had a thickness of about 40 μm prior tofiring. Thus, the second ceramic layer 20 b had a thickness of about 220μm prior to firing.

In Examples 5 to 24, as with Example 1, all of the layers in the firstand second ceramic layers 20 a and 20 b were defined by the ceramiclayers 22 a and 22 b having a low rare-earth element concentration, thefirst and second ceramic layers 20 a and 20 b being included in theouter layer portions 14 and being arranged vertically. In Examples 12 to17 and Example 24, a Mn concentration in the material for the greensheets having a low rare-earth element concentration and defining theoutermost layer portions, the green sheets to be formed into the ceramiclayers 22 a and 22 b, was lower than a Mn concentration in the greensheets for the inner layers.

Regarding the rare-earth element in the green sheets having a lowrare-earth element concentration, Gd was used in Example 8. Y was usedin Example 9. La was used in Example 10. Dy was used in all otherexamples.

Regarding the main component of the green sheets for the inner layers, a(Ba_(0.93)Ca_(0.07))TiO₃ powder was used in Example 18. A(Ba_(0.99)Sr_(0.01))TiO₃ powder was used in Example 19. ABa(Ti_(0.98)Zr_(0.02))O₃ powder was used in Example 20. ABa(Ti_(0.99)Hf_(0.01))O₃ powder was used in Example 21.

Regarding the main-component powder for the green sheets having a lowrare-earth element concentration, a (Ba_(0.93)Ca_(0.07)) TiO₃ powder wasused in Example 18. A (Ba_(0.99)Sr_(0.01))TiO₃ powder was used inExample 19. A Ba(Ti_(0.98)Zr_(0.02))O₃ powder was used in Example 20. ABa(Ti_(0.99)Hf_(0.01))O₃ powder was used in Example 21. A(Ba_(0.93)Ca_(0.07))TiO₃ powder was used in Example 22.

In Comparative Examples 1 to 6, as with conventional multilayer ceramiccapacitors, all of the layers in the first and second ceramic layers 20a and 20 b were defined by the intermediate ceramic layers 24 a and 24b, the first and second ceramic layers 20 a and 20 b being included inthe outer layer portions 14 and being arranged vertically.

Regarding the main-component powder for the green sheets for the innerlayers, a (Ba_(0.93)Ca_(0.07))TiO₃ powder was used in ComparativeExample 2. A (Ba_(0.99)Sr_(0.01))TiO₃ powder was used in ComparativeExample 3. A Ba(Ti_(0.98)Zr_(0.02))O₃ powder was used in ComparativeExample 4. A Ba(Ti_(0.99)Hf_(0.01))O₃ powder was used in ComparativeExample 5.

Regarding the main-component powder for the green sheets for the outerlayers, a (Ba_(0.93)Ca_(0.07))TiO₃ powder was used in ComparativeExample 2. A (Ba_(0.99)Sr_(0.01))TiO₃ powder was used in ComparativeExample 3. A Ba(Ti_(0.98)Zr_(0.02))O₃ powder was used in ComparativeExample 4. A Ba(Ti_(0.99)Hf_(0.01))O₃ powder was used in ComparativeExample 5. A (Ba_(0.93)Ca_(0.07))TiO₃ powder was used in ComparativeExample 6.

In Examples 1 to 24 and Comparative Examples 1 to 6, the raw-materialpowders in the prepared slurries for sheet formation were dissolved inan acid and analyzed by ICP emission spectroscopy. The resultsdemonstrated that the raw-material powders had the same or substantiallythe same compositions as those described in Table 1.

In Examples 1 to 24 and Comparative Examples 1 to 6, the ceramic layersfor the inner layers (which were not isolated from the inner Nielectrodes because it is difficult to perform isolation from the innerelectrodes) and the outermost layer portions were extracted by grindingfrom the multilayer bodies (ceramic main bodies) after the removal ofthe outer electrodes of the multilayer ceramic capacitors produced. Theywere dissolved in an acid and analyzed by ICP emission spectroscopy. Theresults demonstrated that the resulting compositions were equal orsubstantially equal to the compositions described in Table 1, except forthe inner-electrode component, Ni.

Evaluation of Characteristics in Example and Comparative Example

Characteristics of the multilayer ceramic capacitors 1 in examples andcomparative examples were evaluated as described below.

In a sample bottle containing 30 mL of a 0.2 mol/L adipic acid solution,40 pieces of the multilayer ceramic capacitors 1 for each capacitor typewere immersed. The sample bottle was sealed and allowed to stand at 85°C. for 120 hours. After cooling, the multilayer ceramic capacitors 1were taken out. The multilayer ceramic capacitors 1 were washed with 20mL of deionized water. Next, the ceramic components, i.e., Ba, Ti Dy,Gd, Y, La, Mg, Mn, and Si, contained in 5 mL of the resulting eluatewere quantified by ICP emission spectroscopy. The total amount of theelements detected was determined in units of vol.

The color of the main surfaces 10 a and 10 b and the color of the sidesurfaces 10 c and 10 d of the multilayer ceramic capacitor 1 werevisually observed.

For each capacitor type, 20 pieces of the multilayer ceramic capacitors1 that have been immersed in the adipic acid solution weresolder-mounted on a printed circuit board with a water-soluble fluxcontaining adipic acid as a main component.

After the solder mounting, the 20 pieces of the multilayer ceramiccapacitors 1 were allowed to stand at room temperature for 24 hours andthen ground to expose a vertical section (LT section) in thelongitudinal direction. Whether a structural defect, such as a crack,occurred or not was observed with an optical microscope.

Twenty pieces of the multilayer ceramic capacitors 1 for each capacitortype were subjected to a high-temperature load reliability test. Thehigh-temperature load reliability test was performed under the followingconditions: a direct-current voltage of 50 V was applied at 170° C. Achange in insulation resistance with time was measured. The point whenthe insulation resistance of each sample was 100 kΩ or less was definedas the point when a failure occurred. The mean time to failure (MTTF)was determined. The case where MTTF was 90 hours or more and less than100 hours was expressed as ◯. The case where MTTF was 150 hours or morewas expressed as ⊙.

Results of Characteristic Evaluation in Examples and ComparativeExamples

Table 1 contains the results of characteristic evaluation in examplesand comparative examples.

TABLE 1 Ceramic layer for inner layer Ceramic layer for outermost layerportion Rare-earth Rare-earth Amount Occurrence Discrim- Main element MnMg Si Main element Mn Mg Si eluted in of ination component Part by Partby Part by Part by component Part by Part by Part by Part by adipic acidstructural of outer powder Type mole mole mole mole powder Type molemole mole mole (μmol) defect layer MTTF Example 1 BaTiO₃ Dy 0.3 0.3 1.01.5 BaTiO₃ Dy 0.2 0.3 1.0 1.5 1.0 0/20 impossible ⊙ Example 2 BaTiO₃ Dy0.3 0.3 1.0 1.5 BaTiO₃ Dy 0.28 0.3 1.0 1.5 2.3 0/20 impossible ⊙ Example3 BaTiO₃ Dy 0.3 0.3 1.0 1.5 BaTiO₃ Dy 0.2 0.3 1.0 1.5 1.5 0/20impossible ⊙ Example 4 BaTiO₃ Dy 0.3 0.3 1.0 1.5 BaTiO₃ Dy 0.2 0.3 1.01.5 1.3 0/20 impossible ⊙ Example 5 BaTiO₃ Dy 0.3 0.3 1.0 1.5 BaTiO₃ Dy0.2 0.3 0.0 1.5 1.1 0/20 impossible ⊙ Example 6 BaTiO₃ Dy 0.3 0.3 1.01.5 BaTiO₃ Dy 0.0 0.3 0.0 1.5 0.8 0/20 impossible ⊙ Example 7 BaTiO₃ Dy1.5 0.3 1.0 1.5 BaTiO₃ Dy 0.0 0.3 1.0 1.5 3.2 0/20 impossible ⊙ Example8 BaTiO₃ Dy 0.3 0.3 1.0 1.5 BaTiO₃ Gd 0.2 0.3 1.0 1.5 1.2 0/20impossible ⊙ Example 9 BaTiO₃ Dy 0.3 0.3 1.0 1.5 BaTiO₃ Y 0.2 0.3 1.01.5 1.4 0/20 impossible ⊙ Example 10 BaTiO₃ Dy 0.3 0.3 1.0 1.5 BaTiO₃ La0.2 0.3 1.0 1.5 1.0 0/20 impossible ⊙ Example 11 BaTiO₃ Dy 0.3 0.08 1.01.5 BaTiO₃ Dy 0.2 0.08 1.0 1.5 0.8 0/20 impossible ⊙ Example 12 BaTiO₃Dy 0.3 0.08 1.0 1.5 BaTiO₃ Dy 0.2 0.05 1.0 1.5 0.9 0/20 possible ⊙Example 13 BaTiO₃ Dy 0.3 0.08 1.0 1.5 BaTiO₃ Dy 0.2 0.0 1.0 1.5 0.9 0/20possible ⊙ Example 14 BaTiO₃ Dy 0.3 0.08 1.0 1.5 BaTiO₃ Dy 0.2 0.0 0.01.5 0.8 0/20 possible ⊙ Example 15 BaTiO₃ Dy 0.3 0.08 1.0 1.5 BaTiO₃ Dy0.0 0.0 1.0 1.5 0.8 0/20 possible ⊙ Example 16 BaTiO₃ Dy 0.3 0.08 1.01.5 BaTiO₃ Dy 0.0 0.0 0.0 1.5 0.8 0/20 possible ⊙ Example 17 BaTiO₃ Dy1.5 0.3 1.0 1.5 BaTiO₃ Dy 0.0 0.05 1.0 1.5 3.7 0/20 possible ⊙ Example18 (Ba_(0.93)Ca_(0.07))TiO₃ Dy 0.3 0.3 1.0 1.5 (Ba_(0.93)Ca_(0.07))TiO₃Dy 0.2 0.3 1.0 1.5 0.8 0/20 impossible ⊙ Example 19(Ba_(0.99)Sr_(0.01))TiO₃ Dy 0.3 0.3 1.0 1.5 (Ba_(0.99)Sr_(0.01))TiO₃ Dy0.2 0.3 1.0 1.5 1.2 0/20 impossible ⊙ Example 20Ba(Ti_(0.98)Zr_(0.02))O₃ Dy 0.3 0.3 1.0 1.5 Ba(Ti_(0.98)Zr_(0.02))O₃ Dy0.2 0.3 1.0 1.5 0.9 0/20 impossible ⊙ Example 21Ba(Ti_(0.99)Hf_(0.01))O₃ Dy 0.3 0.3 1.0 1.5 Ba(Ti_(0.99)Hf_(0.01))O₃ Dy0.2 0.3 1.0 1.5 1.0 0/20 impossible ⊙ Example 22 BaTiO₃ Dy 0.3 0.3 1.01.5 (Ba_(0.93)Ca_(0.07))TiO₃ Dy 0.2 0.3 1.0 1.5 1.0 0/20 impossible ⊙Example 23 BaTiO₃ Dy 0.28 0.3 1.0 1.5 BaTiO₃ Dy 0.0 0.3 1.0 1.5 0.8 0/20impossible ◯ Example 24 BaTiO₃ Dy 0.3 0.3 1.0 1.5 BaTiO₃ Dy 0.2 0.27 1.01.5 1.1 0/20 possible ⊙ * Comparative BaTiO₃ Dy 0.3 0.3 1.0 1.5 BaTiO₃Dy 0.3 0.3 1.0 1.5 10.3 20/20  impossible ⊙ Example 1 * Comparative(Ba_(0.93)Ca_(0.07))TiO₃ Dy 0.3 0.3 1.0 1.5 (Ba_(0.93)Ca_(0.07))TiO₃ Dy0.3 0.3 1.0 1.5 10.1 20/20  impossible ⊙ Example 2 * Comparative(Ba_(0.99)Sr_(0.01))TiO₃ Dy 0.3 0.3 1.0 1.5 (Ba_(0.99)Sr_(0.01))TiO₃ Dy0.3 0.3 1.0 1.5 13.4 20/20  impossible ⊙ Example 3 * ComparativeBa(Ti_(0.98)Zr_(0.02))O₃ Dy 0.3 0.3 1.0 1.5 Ba(Ti_(0.98)Zr_(0.02))O₃ Dy0.3 0.3 1.0 1.5 11.3 20/20  impossible ⊙ Example 4 * ComparativeBa(Ti_(0.99)Hf_(0.01))O₃ Dy 0.3 0.3 1.0 1.5 Ba(Ti_(0.99)Hf_(0.01))O₃ Dy0.3 0.3 1.0 1.5 10.7 20/20  impossible ⊙ Example 5 * Comparative BaTiO₃Dy 0.3 0.3 1.0 1.5 (Ba_(0.93)Ca_(0.07))TiO₃ Dy 0.3 0.3 1.0 1.5 12.020/20  impossible ⊙ Example 6 * Outside the scope of the presentinvention

Table 1 indicates that in Examples 1 to 24, the amount eluted in adipicacid (organic acid) is suppressed because the main surfaces 10 a and 10b of the multilayer ceramic capacitors 1 are defined by the ceramiclayers 22 a and 22 b having a low rare-earth element concentration. Thereason for this is that the rare-earth elements in the intermediateceramic layers 24 a and 24 b are less likely to be eluted from the mainsurfaces 10 a and 10 b. This also leads to a reduction in the occurrenceof the structural defect after solder mounting.

Regarding the multilayer ceramic capacitors 1 in Examples 1 to 24, thereason the resistance to elution is improved is considered as follows:the ceramic layers 22 a and 22 b having a low rare-earth elementconcentration are not easily dissolved in a water-soluble flux(containing an organic acid), thus improving acid resistance. In otherwords, the rare-earth elements diffuse into the perovskite-typecompounds during firing. The rates of diffusion thereof are very low.Thus, the concentrations of the rare-earth elements are likely toincrease at grain boundaries, so that the rare-earth elementsprecipitate easily as segregated phases. Ceramic components primarilycontaining the additive elements also tend to concentrate at a portionwith a high rare-earth element concentration. Such grain boundaries andsegregated phases are highly soluble in the water-soluble flux.Therefore, reductions in the concentrations of the added rare-earthelements result in an improvement in the resistance to elution in thewater-soluble flux.

The results of Example 4 demonstrate that even where the ceramic layers22 a having a low rare-earth element concentration are not arranged inthe first ceramic layer 20 a and where the ceramic layers 22 b having alow rare-earth element concentration are arranged in only the secondceramic layer 20 b, the advantageous effects of preferred embodiments ofthe present invention are achieved.

In each of Examples 12 to 17 and Example 24, the Mn concentration in thematerial for the green sheets having a low rare-earth elementconcentration and being formed into the ceramic layers 22 a and 22 b,was lower than the Mn concentration in the green sheets for the innerlayers. Thus, the color of the main surfaces 10 a and 10 b of themultilayer ceramic capacitor 1 is visually discriminable from the colorof the side surfaces 10 c and 10 d. The color of the main surfaces 10 aand 10 b (the ceramic layers 22 a and 22 b having a low rare-earthelement concentration) is lighter than that of the side surfaces 10 cand 10 d (primarily, the intermediate ceramic layers 24 a and 24 b).Thus, the main surfaces 10 a and 10 b are easily discriminable from theside surfaces 10 c and 10 d.

In each of Examples 12 to 17 and Example 24, the reason the color of themain surfaces 10 a and 10 b (the ceramic layers 22 a and 22 b having alow rare-earth element concentration) is lighter than that of the sidesurfaces 10 c and 10 d (primarily, the ceramic layers 16 for the innerlayers) is as follows: Mn imparts resistance to reduction to adielectric ceramic material such that the dielectric ceramic material isnot converted into a semiconductor even if the dielectric ceramicmaterial is fired at a low oxygen partial pressure. Moreover, Mn givesrise to color in the multilayer ceramic capacitor (when BaTiO₃ is usedas a main component, the capacitor has a brownish color). Thus, areduction in the amount of added Mn lightens the color.

The results of the high-temperature load reliability test for themultilayer ceramic capacitors 1 in Examples 1 to 24 demonstrated thateach of the capacitors in all examples except Example 23 exhibitedsatisfactory results and had an MTTF of 150 hours or more.

The present invention is not limited to the foregoing preferredembodiments. Various changes may be made within the scope of theinvention. Furthermore, the thicknesses of the ceramic layers, thenumber of layers, the area of the counter electrodes, and the externaldimensions of the multilayer ceramic capacitors, for example, are notlimited to the preferred embodiments described herein.

While preferred embodiments of the present invention have been describedabove, it is to be understood that variations and modifications will beapparent to those skilled in the art without departing from the scopeand spirit of the present invention. The scope of the present invention,therefore, is to be determined solely by the following claims.

What is claimed is:
 1. A multilayer ceramic capacitor comprising: aceramic main body including: a first outer layer portion including firstceramic layers; a second outer layer portion including second ceramiclayers; an inner layer portion including third ceramic layers and innerelectrodes arranged at a plurality of interfaces between at least someof the third ceramic layers; and outer electrodes arranged on surfacesof the ceramic main body and electrically connected to the innerelectrodes; wherein the first outer layer portion and the second outerlayer portion are arranged vertically so as to sandwich the inner layerportion therebetween; the third ceramic layers contain a perovskite-typecompound represented by ABO₃, where A contains one or more of Ba, Sr,and Ca; B contains one or more of Ti, Zr, and Hf; and O representsoxygen, and a rare-earth element; an outermost layer portion of at leastone of the first and the second outer layer portions including at leasta portion of a surface of the ceramic main body contains aperovskite-type compound represented by A′B′O₃, where A′ contains one ormore of Ba, Sr, and Ca; B′ contains one or more of Ti, Zr, and Hf; and Orepresents oxygen, and optionally a rare-earth element that is the sameor different as the rare-earth element of the third ceramic layers; amol concentration (C_(R)) of the rare-earth element in the third ceramiclayers is greater than a mol concentration (C_(r)) of the rare-earthelement in the outermost layer portion, C_(R)>C_(r), inclusive ofC_(r)=0; the mol concentration (C_(R)) is about 0.3 parts by mole ormore with respect to 100 parts by mole of total amount of Ti, Zr, and Hfincluded in the third ceramic layers; and the mol concentration (C_(r))is less than about 0.3 parts by mole with respect to 100 parts by moleof total amount of Ti, Zr, and Hf included in the outermost layerportions.
 2. The multilayer ceramic capacitor according to claim 1,wherein an entirety of the surface of the ceramic main body contains theperovskite-type compound represented by A′B′O₃.
 3. A multilayer ceramiccapacitor comprising: a ceramic main body including: a first outer layerportion including first ceramic layers; a second outer layer portionincluding second ceramic layers; an inner layer portion including thirdceramic layers and inner electrodes arranged at a plurality ofinterfaces between at least some of the third ceramic layers; and outerelectrodes arranged on surfaces of the ceramic main body andelectrically connected to the inner electrodes; wherein the first outerlayer portion and the second outer layer portion are arranged verticallyso as to sandwich the inner layer portion therebetween; the thirdceramic layers contain a perovskite-type compound represented by ABO₃,where A contains one or more of Ba, Sr, and Ca; B contains one or moreof Ti, Zr, and Hf; and O represents oxygen, a rare-earth element, andMn; an outermost layer portion of at least one of the first and thesecond outer layer portions including a portion of a surface of theceramic main body contains a perovskite-type compound represented byA′B′O₃, where A′ contains one or more of Ba, Sr, and Ca; B′ contains oneor more of Ti, Zr, and Hf; and O represents oxygen, and optionally Mnand a rare-earth element that is the same or different as the rare-earthelement of the third ceramic layers; a mol concentration (C_(R)) of therare-earth element in the third ceramic layers is greater than a molconcentration (C_(r)) of the rare-earth element in the outermost layerportion, C_(R)>C_(r), inclusive of C_(r)=0; and a mol concentration(C_(M)) of Mn in the third ceramic layers is greater than a molconcentration (C_(m)) of Mn in the outermost layer portion, C_(M)>C_(m)(inclusive of C_(m)=0).
 4. The multilayer ceramic capacitor according toclaim 3, wherein an entirety of the surface of the ceramic main bodycontains the perovskite-type compound represented by A′B′O₃.
 5. Amultilayer ceramic capacitor comprising: a ceramic main body including:a first outer layer portion including first ceramic layers; a secondouter layer portion including second ceramic layers; an inner layerportion including third ceramic layers and inner electrodes arranged ata plurality of interfaces between at least some of the third ceramiclayers; and outer electrodes arranged on surfaces of the ceramic mainbody and electrically connected to the inner electrodes; wherein thefirst outer layer portion and the second outer layer portion arearranged vertically so as to sandwich the inner layer portiontherebetween; the third ceramic layers contain a perovskite-typecompound represented by ABO₃, where A contains one or more of Ba, Sr,and Ca; B contains one or more of Ti, Zr, and Hf; and O representsoxygen, a rare-earth element, and Mn; and only the second outer layerportion of the first and second outer layer portions includes each offeatures (a), (b), (c) and (d): (a) an outermost layer portion of atleast one of the first and the second outer layer portions including aportion of a surface of the ceramic main body contains a perovskite-typecompound represented by A′B′O₃, where A′ contains one or more of Ba, Sr,and Ca, B′ contains one or more of Ti, Zr, and Hf, and O representsoxygen, and optionally Mn and a rare-earth element that is the same ordifferent than the rare-earth element of the third ceramic layers; (b) amol concentration (C_(R)) of the rare-earth element in the third ceramiclayers is greater than a mol concentration (C_(r)) of the rare-earthelement in the outermost layer portion, C_(R)>C_(r), inclusive ofC_(r)=0; and (c) a mol concentration (C_(M)) of Mn in the third ceramiclayers is greater than a mol concentration (C_(m)) of Mn in theoutermost layer portion, C_(M)>C_(m) (inclusive of C_(m)=0); and (d) anintermediate ceramic layer is arranged between the outermost layerportion and the inner layer portion, and the intermediate ceramic layerhas a different composition from the outermost layer portion.
 6. Themultilayer ceramic capacitor according to claim 5, wherein the firstouter layer portion includes any one, two or three of features (a), (b),(c) and (d), and wherein feature (a) is an outermost layer portion ofthe first outer layer portion including a portion of a surface of theceramic main body contains a perovskite-type compound represented byA′B′O₃, where A′ contains one or more of Ba, Sr, and Ca, B′ contains oneor more of Ti, Zr, and Hf, and O represents oxygen, and optionally Mnand a rare-earth element that is the same or different than therare-earth element of the third ceramic layers.
 7. The multilayerceramic capacitor according to claim 5, wherein an entirety of thesurface of the ceramic main body contains the perovskite-type compoundrepresented by A′B′O₃.
 8. The multilayer ceramic capacitor according toclaim 5, wherein the mol concentration (C_(r)) of the rare-earth elementin the outermost layer portion is smaller than a mol concentration ofthe rare-earth element in the outermost layer portion of the first outerlayer portion including the portion of the surface of the ceramic mainbody.